CN104105730B - The manufacture method of cured coating film, blooming and the manufacture method of film shaped body - Google Patents
The manufacture method of cured coating film, blooming and the manufacture method of film shaped body Download PDFInfo
- Publication number
- CN104105730B CN104105730B CN201380008738.6A CN201380008738A CN104105730B CN 104105730 B CN104105730 B CN 104105730B CN 201380008738 A CN201380008738 A CN 201380008738A CN 104105730 B CN104105730 B CN 104105730B
- Authority
- CN
- China
- Prior art keywords
- methyl
- mentioned
- film
- urethane acrylate
- cured coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
- C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention provides a kind of and does not comprise Photoepolymerizationinitiater initiater and ultra-violet solidified excellence and can be used in the ultra-violet solidified urethane acrylate compositions of optical applications of requirement high transparent.nullDescribed ultra-violet solidified urethane acrylate compositions is the ultra-violet solidified urethane acrylate compositions of the urethane acrylate oligomer (E) containing molecular end with (methyl) acryloyl group，The carbamate prepolymer (C) that described urethane acrylate oligomer (E) has NCO by making (methyl) acrylic compounds (D) with hydroxyl and molecular end carries out additive reaction and obtains，Described carbamate prepolymer (C) obtains by making the polyhydric alcohol (A) without aromatic backbone and do not have polyisocyanate (B) reaction of aromatic backbone，Wherein，Described ultra-violet solidified urethane acrylate compositions contain 0.2～80 mass % selected from ketone series solvent、At least one in amide series solvent and haloalkyl series solvent does not have the organic solvent (F) of aromatic backbone，And do not contain Photoepolymerizationinitiater initiater.
Description
Technical field
The present invention relates to the manufacture method of cured coating film, blooming and the manufacture method of film shaped body.
More specifically, the present invention relates to manufacture with to existing ultra-violet solidified resin composition irradiation ultraviolet radiation
The manufacture method of the cured coating film that the method for cured coating film is different, the manufacture method of described cured coating film is to not comprising light
Polymerization initiator and comprise specific organic solvent as retarder thinner, promptly solidified by ultraviolet irradiation, can
Suppression gained solidfied material through time xanthochromia, pollution-free to contactant and screening characteristics or the property such as formability of excellence can be shown
Can ultra-violet solidified urethane acrylate compositions irradiation ultraviolet radiation cured coating film manufacture method, have on
The blooming stating cured coating film and the manufacturer of the film shaped body on base material with above-mentioned cured coating film (such as sheet, film)
Method.
Background technology
All the time, it is possible to and irradiate consolidate by ultraviolet, electron ray, lonizing radiation, infrared ray isoreactivity energy-ray
The light-cured resin changed has been used for various field.In above-mentioned light-cured resin, uv curing resin is with poly-
Conjunction property compound (monomer, oligomer, polymer etc.) is raw material and obtains, and owing to these polymerizable compounds pass through ultraviolet
Line irradiates and is susceptible to curing reaction, therefore there is not volatile ingredient, thus is subject to as the improvement measure of problem of environmental pollution
To attracting attention.
But, the energy of light is determined by " wavelength ", i.e. " color ", it is known that there is formula (1) between energy and the wavelength of light
Relation.
Energy (eV)=1240/ wavelength (nm) formula (1) of light
Such as, it is seen that the wavelength region of light is (red) 700nm～(royal purple) 400nm, and the energy equivalence of light is in (red)
1.77eV～(royal purple) 3.0eV.
For the wavelength and energy of usual mercury lamp used in the curing reaction of uv curing resin, high
Pressure mercury lamp is near 360nm (3.4eV), and low pressure mercury lamp is near 255nm (4.9eV).
But, the scope that Cohesive Energy is 5～8eV of most materials, excitation energy is more than 4eV, therefore, ultraviolet
The photon in region does not have enough energy for the initiation of macromolecular polymerization reaction.
Therefore, generate free radical to be excited by ultraviolet, " Photoepolymerizationinitiater initiater " (also referred to as
“photoinitiator”.) existence be indispensable.
In above-mentioned polymerizable compound, for have (methyl) acryloyl group reactive compounds (monomer, oligomer,
Polymer etc.) for, it is irradiated by ultraviolet and carries out cross-linking reaction well and solidify, and therefore, is widely used.
In this curing system, it is necessary to use and irradiated by ultraviolet and the Photoepolymerizationinitiater initiater of free radical can be generated, above-mentioned photopolymerization
Initiator causes the radical polymerization of above-mentioned (methyl) acryloyl group to form solidfied material.Therefore, in the painting of radically curing
In the fields such as material, printing-ink, formed products, reactive compounds and the Photoepolymerizationinitiater initiater with (methyl) acryloyl group become
The essential component of ultra-violet solidified compositions.
But, in this existing ultra-violet solidified compositions, the unreacted reactant of Photoepolymerizationinitiater initiater, analyte are residual
It is stored in film, formed body etc., therefore causes various problem.Specifically, above-mentioned unreacted reactant, analyte migrate and (are directed to
The material diffusion transfer that resin is interior or adjacent.) to film coated surface or formed body surface, when by film or formed products stacking, deposit
Problem etc. as follows: pollute the object contacted with this film or formed products；Or, in the packaging of food or pharmaceuticals etc.
In field, above-mentioned unreacted reactant or analyte become the impurity that should remove.
It addition, as the serious problems caused by Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater after decomposition in conjunction with time
Being changed to yellow substance, produce the yellowing of solidfied material, become in the optical applications of the transparency for requiring high-quality is thin
The main cause that the performance of film formed body (film, sheet), fiber, coating etc. reduces.Especially for the photopolymerization containing aromatic rings
For initiator, its aromatic rings absorb luminous energy, produce free radical efficiently, therefore more used, but its in conjunction with
Shi Chengwei is derived from the quinoid structure of aromatic rings, it may be said that define the chromophoric group of stronger yellow.
In order to improve the problems referred to above, it is proposed that various schemes.
For example, as it is known that make beta-diketonate compound or beta-diketone compound and polyfunctional acrylic ester in the existence of catalyst
Under, and, a) reaction temperature be 60～140 DEG C, b) acryloyl group in above-mentioned ester relative to above-mentioned beta-diketonate compound or
The ratio (acryloyl group: beta-dicarbonyl) of the beta-dicarbonyl in beta-diketone compound is the light of reaction under conditions of 2.5: 1～20: 1
The manufacture method of curable resin is (for example, referring to patent documentation 1.).
According to above-mentioned patent documentation 1, can industrially productivity ratio manufacture well in the situation without Photoepolymerizationinitiater initiater
Under show the curable of excellence, solidfied material disappear viscosity and hardness excellent, this external for curing reaction before show good
The light-cured resin of storage-stable, be suitable to the photopolymerization in UV curable coating, printer's ink liquid, sheet and formed products purposes
The manufacture of property resin.
But, the manufacture method of patent documentation 1 light-cured resin obtained is in the deterioration of (1) storage-stable and storage
The manufacture views such as Shi Yichang thickening, the generation yellowing of (2) solidfied material and quality aspect existing problems.
Additionally, it is known that the light being made up of the solidfied material of the polymerizable composition, polymerizable composition comprising carbamate (methyl) acrylate
Learn sheet (for example, referring to patent documentation 2.).
According to above-mentioned patent documentation 2, containing substantially no polymerization initiator, photocured product is for irradiating obtained by electron ray
Photocured product, the transparency is high, has an elastomer of appropriateness, and has good formability, processability, thermostability, weatherability
(difficult xanthochromia).
But, for the optical sheet of patent documentation 2, in the case of being irradiated by ultraviolet and solidifying, then
Photoepolymerizationinitiater initiater must be contained, thus there is the problem that solidfied material occurs yellowing because of Photoepolymerizationinitiater initiater.
It addition, in the case of not containing Photoepolymerizationinitiater initiater, need electronbeam irradiation, but electron beam irradiation device
Costliness, and need to arrange screening arrangement, thus be industrially not appropriate for.Additionally, electronbeam irradiation easily causes base material
Deterioration, and especially solidfied material is the thickest, the most more needs the maximization of electron beam irradiation device and masking device, thus at equipment
Present aspect is become to there is also problem.
For the ultra-violet solidified urethane acrylate compositions in the past used, about
The cured coating film of gained, the poor performance such as its yellowing resistance, the viscosity that disappears (without cohesive) of applicator surface, the transparency, for and practicality
Aspect there is also the problem that should solve.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-163041 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-164363 publication
Summary of the invention
Invent problem to be solved
It is an object of the invention to, it is provided that to can be used in especially requiring the optical applications of the transparency of high-quality (such as
Film, sheet, fiber, coating material etc.) in one ultra-violet solidified urethane acrylate compositions irradiation ultraviolet radiation
The manufacture method of cured coating film, the blooming with above-mentioned cured coating film and the manufacture method of film shaped body, above-mentioned ultraviolet
Problem is stated: the unreacted reactant of Photoepolymerizationinitiater initiater or analyte in the absence of line curable urethane acrylate compositions
Migration (diffusion transfer), to film coated surface or formed products surface, is polluted and this film or shaping when by film or formed products stacking
The object of product contact；Or in the packaging field of food or pharmaceuticals, above-mentioned unreacted reactant or analyte become and should remove
Impurity；Or the Photoepolymerizationinitiater initiater after Fen Xieing in conjunction with time be changed to yellow substance, make the yellow chromaticity of solidfied material deteriorate.
For the method solving problem
The present inventor etc. conduct in-depth research to solve above-mentioned problem, it was found that utilize containing following point
Sub-end has the urethane acrylate oligomer of (methyl) acryloyl group and specific organic solvent, and does not contains
The manufacture of the cured coating film of the ultra-violet solidified urethane acrylate compositions irradiation ultraviolet radiation of Photoepolymerizationinitiater initiater
Method, such that it is able to obtain ultraviolet irradiate time and through time xanthochromia excellence minimum, transparent and will not be because of Photoepolymerizationinitiater initiater
Unreacted reactant or the migration of analyte and pollute the cured coating film of the object contacted with film or formed body, this completes this
Invention, wherein, described urethane acrylate oligomer by make to have (methyl) acrylic compounds of hydroxyl with
Following molecular end has the carbamate prepolymer of NCO and carries out additive reaction and obtain, described carbamate
Prepolymer obtains by making the polyhydric alcohol without aromatic backbone and do not have the polyisocyanate reaction of aromatic backbone.
That is, the present invention relates to the manufacture method of a kind of cured coating film, it is characterised in that be will to have containing molecular end
The urethane acrylate oligomer (E) of (methyl) acryloyl group and selected from ketone series solvent, amide series solvent and alkyl halide
At least one in base system solvent does not have the ultra-violet solidified carbamate propylene of the organic solvent (F) of aromatic backbone
Acid ester composite is coated on base material and forms film, then irradiation ultraviolet radiation, then makes above-mentioned organic solvent (F) volatilization obtain
Obtaining the manufacture method of the cured coating film of cured coating film, described urethane acrylate oligomer (E) is by making have hydroxyl
(methyl) acrylic compounds (D) and the molecular end carbamate prepolymer (C) with NCO add
Becoming reaction to obtain, described carbamate prepolymer (C) is by making the polyhydric alcohol (A) without aromatic backbone and not having
The polyisocyanate (B) of aromatic backbone is reacted and is obtained, wherein, and above-mentioned ultra-violet solidified urethane acrylate group
Compound contains the described organic solvent (F) of 0.2～80 mass %, and does not contains Photoepolymerizationinitiater initiater.
The present invention relates to a kind of film shaped body, it is characterised in that there is on base material the system by above-mentioned cured coating film
Make cured coating film obtained by method.
The present invention relates to a kind of blooming, it is characterised in that be to there is the manufacture method by above-mentioned cured coating film and obtain
The blooming of cured coating film, wherein, the total light recorded according to JIS K7361-1 during thickness 100 μm of above-mentioned cured coating film
Line absorbance is more than 92%.
The present invention relates to the manufacture method of a kind of film shaped body, it is characterised in that be to have on base material by above-mentioned
The manufacture method of the film shaped body of cured coating film obtained by the manufacture method of cured coating film, wherein, by above-mentioned ultraviolet curing
Property urethane acrylate compositions is coated on base material and forms film, irradiation ultraviolet radiation and make above-mentioned curing of coating,
Then above-mentioned organic solvent (F) is made to volatilize.
Invention effect
The manufacture method of the cured coating film of the present invention is by the ultra-violet solidified amino not containing Photoepolymerizationinitiater initiater
Formic acid esters acrylate composition irradiation ultraviolet radiation and show the photo-curable of excellence, and the transparency of the cured coating film of gained
Excellence, will not occur through time xanthochromia, the object contacted with cured coating film will not be polluted, it is thus possible, for instance at optics component
The broad spectrum such as (film, sheet etc.), fiber, coating, fixative, packaging material, grinding agent, road pavement agent, electric material
Field in useful.
Detailed description of the invention
<ultra-violet solidified urethane acrylate compositions>
Ultra-violet solidified urethane acrylate compositions used in the present invention, is containing following molecule end
End has the ultra-violet solidified carbamate propylene of the urethane acrylate oligomer (E) of (methyl) acryloyl group
Acid ester composite, above-mentioned urethane acrylate oligomer (E) is by making (methyl) the acrylic compounds chemical combination with hydroxyl
Thing (D) with make the polyhydric alcohol (A) without aromatic backbone and do not have the polyisocyanate (B) of aromatic backbone react and
The molecular end obtained has the carbamate prepolymer (C) of NCO and carries out additive reaction and obtain, and above-mentioned ultraviolet
Line curable urethane acrylate compositions contain 0.2～80 mass % selected from ketone series solvent, amide series solvent and
At least one organic solvent (F) in haloalkyl series solvent, and do not contain any Photoepolymerizationinitiater initiater.
Hereinafter, detailed to above-mentioned (A)～(F) constituting above-mentioned ultra-violet solidified urethane acrylate compositions
Illustrate.
(A) not there is the polyhydric alcohol of aromatic backbone
As the above-mentioned polyhydric alcohol (A) without aromatic backbone used in the present invention, there are aliphatic polyol and fat
Ring race polyhydric alcohol, for example, it is possible to list PEPA, polyether polyol, polycarbonate polyol, low molecular weight diols
Deng.
The dicarboxylic acids used in the manufacture of above-mentioned PEPA is the dicarboxylic acids without aromatic backbone, such as, and can
With list succinic acid, adipic acid, Azelaic Acid, decanedioic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-Pentamethylene. two
Carboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid etc..They can be used alone, it is also possible to and use two or more.
The glycol used in the manufacture of above-mentioned PEPA is the glycol without aromatic backbone, for example, it is possible to row
Enumerate: ethylene glycol, 1,2-PD, 1,3-PD, 1,3 butylene glycol, BDO, 1,5-PD, 1,6-oneself two
Alcohol, neopentyl glycol, trimethylene, diethylene glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, 3-methyl-
1,5-PD, 2-butyl-2-ethyl-1,3-PD, 2-methyl isophthalic acid, the aliphatic diol class such as ammediol；Isosorbide-5-Nitrae-hexamethylene
The alicyclic diol classes etc. such as glycol, 1,4-CHDM, hydrogenated bisphenol A.They can be used alone, it is also possible to and with 2
More than Zhong.
Additionally, as the raw material of above-mentioned PEPA, such as can also use: glycerol, trimethylolethane, three hydroxyls
The alcohols such as methylpropane, sorbitol, sucrose；Or amine etc..They can be used alone, it is also possible to and use two or more.
The number-average molecular weight of above-mentioned PEPA is (hereinafter referred to as " Mn ".) preferably take into account NCO terminal amino group
The target viscosities of urethane prepolymer (C) is set, the scope of preferably 500～3500, more preferably 600～2500
Scope.If the Mn of above-mentioned PEPA is above-mentioned scope, the most above-mentioned NCO terminal carbamate ester prepolymer will not
Occur extreme viscosity to rise, the carbamate prepolymer of the melt viscosity of appropriateness can be obtained.
Above-mentioned PEPA also include and obtain with dicarboxylic acids other than the above, glycol, diamidogen etc. polyester-diol,
Polyamide polyester glycol etc..
It addition, as above-mentioned polyether polyol, for example, it is possible to list Polyethylene Glycol (PEG), polypropylene glycol (PPG), gather
Ethylidene propylene glycol (PEPG), polytetramethylene glycol (PTMG), 2-methyl isophthalic acid, 3-propane adipate ester, 3-methyl isophthalic acid, 5 penta
Alkane adipate ester etc., wherein, the preferably polytetramethylene glycol PTMG of 650～2000 (Mn be).Above-mentioned polyether polyol is permissible
Have straight chain, side chain, ring-type in any one structure.
The Mn of above-mentioned polyether polyol is preferably the scope of 500～3500, the scope of more preferably 600～3000.On if
The Mn stating polyether polyol is above-mentioned scope, and the most above-mentioned NCO terminal carbamate ester prepolymer will not occur extreme
Viscosity rises, and can obtain the carbamate prepolymer of the melt viscosity of appropriateness.
In the present invention, it is also possible to use lactone (such as 6-caprolactone, gamma-butyrolacton etc.) and polytetramethylene glycol
(PTMG), the above-mentioned polyether polyol such as polypropylene glycol (PPG), Polyethylene Glycol (PEG) carries out obtained by ring opening polyaddition polynary
Alcohol etc..
It addition, as above-mentioned polycarbonate polyol, it is, for example possible to use carbonic acid and aliphatic polyol is made to be esterified
Polycarbonate polyol etc. obtained by reaction.Specifically, can list 1,3-PD, BDO, 1,6-oneself two
Glycol and dimethyl carbonate, the phosgenes such as alcohol, diethylene glycol, Polyethylene Glycol, polypropylene glycol or polytetramethylene glycol (PTMG)
Deng product etc..They can be used alone, it is also possible to and use two or more.
It addition, as above-mentioned low molecular weight diols, for example, it is possible to list: ethylene glycol (EG), 1,2-PD, 1,3-
Propylene glycol, 1,3 butylene glycol, BDO, 1,5-PD, 1,6-hexanediol, neopentyl glycol, diethylene glycol, three second two
Alcohol, TEG, dipropylene glycol, tripropylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-butyl-2-ethyl-1,3-PD, 2-first
The glycols such as base-1,3-PD；Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, hydrogenated bisphenol A etc. are alicyclic
Di-alcohols；3 officials such as glycerol, trimethylolpropane, tetramethylolmethane can have the compound etc. of hydroxyl above, wherein, excellent
Select diethylene glycol (DEG).Above-mentioned low molecular weight diols can have straight chain, side chain, any one ring-type structure.
The molecular weight of above-mentioned low molecular weight diols is preferably the scope of 50～300, the scope of more preferably 50～200.If
The molecular weight of above-mentioned low molecular weight diols is above-mentioned scope, then as polyhydric alcohol (A) and with in the case of, can be more effective
Ground controls reactivity, and formability (yield rate, shaping inequality) becomes the best.
As the above-mentioned polyhydric alcohol (A) without aromatic backbone, such as, can also use opening by caprolactone monomer
Cyclopolymerization and obtain polycaprolactone polyol, acrylic polyol (ア Network リ Le Port リ オ mono-Le), polyolefin polyhydric alcohol, castor
Oleum Sesami system polyhydric alcohol etc..
Furthermore it is also possible to and use polyamines.As above-mentioned polyamines, such as can use ethylenediamine, isophorone diamine, 4,
4 '-dicyclohexyl methyl hydride diamidogen, diamino-cyclohexane, methyl diamino-cyclohexane, piperazine, norborene diamidogen etc..
Additionally, do not hindering in the range of the purpose of the present invention, can be used together other not with above-mentioned polyhydric alcohol (A)
There is the polyhydric alcohol of aromatic rings skeleton.
(B) not there is the polyisocyanate of aromatic backbone
It follows that the following polyisocyanate (B) without aromatic backbone to using in the present invention illustrates.
Above-mentioned NCO terminal carbamate ester prepolymer (C) above-mentioned can not have aromatic series bone by using
The polyhydric alcohol (A) of frame and not there is the polyisocyanate (B) of aromatic backbone, and make it react and obtain according to known methods
Arriving, its reaction method, reaction condition are not particularly limited.In the present invention, by above-mentioned polyhydric alcohol (A) and above-mentioned polyisocyanate
(B) NCO terminal carbamate ester prepolymer (C) synthesized does not has aromatic backbone.
It should be noted that " polyisocyanate " described in the present invention refers to the isocyanates in molecule with more than 2
Base is (hereinafter also referred to as NCO base.) compound.
As the above-mentioned polyisocyanate (B) without aromatic backbone, it is possible to use known aliphatic poly Carbimide.
Any one in ester and ester ring type polyisocyanate.They can be used alone, it is also possible to and use two or more.
As above-mentioned aliphatic polymeric isocyanate, such as, can list hexamethylene diisocyanate (HDI), dimeric dibasic acid
Diisocyanate, lysinediisocyanate etc..
As above-mentioned alicyclic polymeric isocyanate, such as, can list isophorone diisocyanate (IPDI), hydrogenation
Methyl diphenylene diisocyanate (hydrogenation MDI), hydrogenation of benzene dimethylene diisocyanate (hydrogenation XDI), hexamethylene two isocyanide
Acid esters, norborene diisocyanate etc..
In the above-mentioned polyisocyanate (B) without aromatic backbone, from giving excellent thermostability and the transparency
Viewpoint considers, such as, HMDI, isophorone diisocyanate etc. are preferably used.
In the present invention, as the above-mentioned polyisocyanate (B) without aromatic backbone, it is necessary to use aliphatic poly different
Cyanate, alicyclic polymeric isocyanate, and use supposition become free radical produce the described later of source not there is aromatic backbone
Organic solvent (F), thus, it is possible to obtain not occurring when ultraviolet irradiates xanthochromia, normally make ultraviolet curing react into
Row, the film of transparency excellence or formed products.
But, as in the past, in the presence of Photoepolymerizationinitiater initiater, only using methyl diphenylene diisocyanate
(MDI), toluene di-isocyanate(TDI) (TDI), tetramethylxylylene diisocyanate etc. have the poly-isocyanide of aromatic backbone
In the case of acid esters (B ') manufactures NCO terminal carbamate ester prepolymer, there is above-mentioned aromatic poly-isocyanate
The absorbance of the aromatic structure being had becomes too high, and utilizing ultraviolet to irradiate the curing reaction implemented cannot fully be carried out,
And the problem that above-mentioned aromatic poly-isocyanate occurs xanthochromia in ultraviolet in irradiating.Be suitable to especially therefore, it is difficult to obtain
Require the ultraviolet curing of the purposes such as the optics component (film, sheet etc.) of the transparency of high-quality, fiber, coating, packaging material
Property urethane acrylate compositions.
(C) molecular end has the carbamate prepolymer of NCO
It follows that in the present invention use molecular end have NCO carbamate prepolymer (C) (with
Under, it is referred to as " NCO terminal carbamate ester prepolymer (C) ".) illustrate.
(hereinafter also referred to " NCO works as the isocyanate equivalent of above-mentioned NCO terminal carbamate ester prepolymer (C)
Amount ") be preferably 100～10000 scope, the scope of more preferably 200～1000.If the NCO equivalent in above-mentioned (C) is above-mentioned
Scope, the exception that the most there is not viscosity rises, and can obtain the carbamate prepolymer that workability is excellent.
It should be noted that " isocyanate equivalent " (unit: g/eq) described in the present invention refers to according to JIS described later
The value that K7301 records.
Above-mentioned NCO terminal carbamate ester prepolymer (C) can be by being had with above-mentioned polyisocyanate (B)
Some NCO bases are relative to above-mentioned polyhydric alcohol (A) had hydroxyl (hereinafter also referred to OH base.) reach superfluous addition, pass through
Known method makes they reactions manufacture.
As being used for obtaining the common reaction method of above-mentioned NCO terminal carbamate ester prepolymer (C), example
As long as used in the polyisocyanate (B) put in reaction vessel, by dropping, in batches, by the gross etc. suitable method throw
Enter to remove the polyhydric alcohol (A) after moisture, the method that the hydroxyl that reaction to polyhydric alcohol (A) is had substantially disappears.
In order to limit smoothly controls the heating in reaction, limit safety and normally react, preferably dropping or in batches
Input method.
The manufacture of above-mentioned NCO terminal carbamate ester prepolymer (C), generally carries out under solvent-free, but also may be used
To carry out reacting in a solvent manufacturing.In the case of reacting in a solvent, do not hinder the solvent of reaction i.e. as long as using
Can, the kind of the solvent used is not particularly limited.After the solvent that reaction is used way the most in the reaction or reaction terminate,
Removed by suitable methods such as heating under reduced pressure, membrane distillation removings.
Reaction condition (temperature, time, pressure etc.) for above-mentioned NCO terminal carbamate ester prepolymer (C)
For, as long as being set in the range of reflex action, product property etc. can normally control, and the most particularly limit
Fixed.Generally, it is preferred to carry out under conditions of reaction temperature 50～90 DEG C, response time 2～24 hours.Pressure can be normal pressure,
Any one in pressurization, decompression.
Reactive mode such as can select batch, the known reactive mode such as semicontinuous, continuous, and is not particularly limited.
It addition, when manufacturing above-mentioned NCO terminal carbamate ester prepolymer (C), ammonia can be used as required
Carbamate catalyst.Above-mentioned catalyst suitably can be carried out in the arbitrary stage during raw material puts into operation, reaction process
Add.It addition, the adding method of catalyst can be by the gross, in batches, continuously etc., and it is not particularly limited.
As above-mentioned urethanation catalyst, it is possible to use known catalyst, such as, can list: three second
The nitrogen-containing compounds such as amine, tri-n-butylamine, benzyl dibutyl amine, triethylenediamine, N-methylmorpholine；Or four titanium butoxide, two fourths
Base stannum oxide, dibutyl tin laurate, 2 ethyl hexanoic acid stannum, zinc naphthenate, cobalt naphthenate, 2 ethyl hexanoic acid zinc, glycolic
The organo-metallic compounds such as molybdenum, potassium acetate, zinc stearate, tin octoate, dibutyl tin laurate；Or iron chloride, zinc chloride
Deng inorganic compound etc..
Generally, reaction is preferably carried out under the inactive gas atmosphere such as nitrogen, argon but it also may in dry air atmosphere
Lower or airtight condition is inferior be not mixed into moisture under conditions of carry out.
In the synthesis of above-mentioned NCO terminal carbamate ester prepolymer (C), the NCO of polyisocyanate (B) works as
The ratio (i.e. [NCO/OH equivalent proportion]) of the OH equivalent of amount and above-mentioned polyhydric alcohol (A) is as long as considering target properties, product property, reaction
Behaviors etc. set.
(D) there is (methyl) acrylic compounds of hydroxyl
It follows that to above-mentioned NCO terminal carbamate ester prepolymer (C) carry out additive reaction, there is hydroxyl
(methyl) acrylic compounds (D) of base illustrates.
In the present invention, (methyl) acrylic compounds (D) with hydroxyl is used, with above-mentioned NCO end
Preferably 5～the scope of 100%, more preferably 10 of the NCO sum of carbamate prepolymer (C)～the scope of 100%
Carry out additive reaction, make them be converted to molecular end and have the urethane acrylate oligomer of (methyl) acryloyl group
(E)。
Be there is the urethane acrylates of (methyl) acryloyl group by the molecular end generated after above-mentioned additive reaction
The double bond that ester oligomer (E) is had, easily makes not contain the ultra-violet solidified carbamate propylene of Photoepolymerizationinitiater initiater
Acid ester composite causes the curing reaction utilizing ultraviolet to irradiate enforcement, and the rapidly-curable that can show excellence (is sent out rapidly
The character of raw solidification), be coated on the shape-retaining ability after base material, mechanical strength, durability, the transparency.
As above-mentioned (methyl) acrylic compounds (D) with hydroxyl, such as, can list (methyl) acrylic acid
2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl fourth
Ester, pentaerythritol triacrylate etc., wherein, such as from above-mentioned ultra-violet solidified urethane acrylate compositions
Ultraviolet is utilized to irradiate the having excellent fast curing implemented and the aspect of the especially mechanical strength raising of the cured coating film of gained
Set out, preferably acrylic acid 2-hydroxy methacrylate (HEA), 2-hydroxyethyl methacrylate.They and to be used alone, it is also possible to and
Use two or more.
(E) molecular end has the urethane acrylate oligomer of (methyl) acryloyl group
It follows that to urethane acrylates that use in the present invention, that molecular end has (methyl) acryloyl group
Ester oligomer (E) is (hereinafter referred to as " urethane acrylate oligomer (E) ".) illustrate.
Above-mentioned urethane acrylate oligomer (E) is obtained as below: relative to above-mentioned NCO terminal amino group
Urethane prepolymer (C) 100 mass parts, preferably in the scope of 0.5～300 mass parts, more preferably in 1.0～100 mass parts
Scope adds (methyl) acrylic compounds (D) with hydroxyl, thus utilizes above-mentioned (methyl) acrylic acid with hydroxyl
Compounds (D), make in above-mentioned carbamate prepolymer (C) NCO sum preferably 5～the scope of 100%,
More preferably 10～100% scope carry out reacting and obtaining.
If making the NCO of above-mentioned NCO terminal carbamate ester prepolymer (C) within the above range with upper
State (methyl) acrylic compounds (D) reaction with hydroxyl, then can obtain rapidly-curable, be coated on the guarantor after base material
The characteristic that type, mechanical strength, durability, base material adaptation etc. are excellent.
The number-average molecular weight (Mn) of above-mentioned urethane acrylate oligomer (E) is preferably the model of 500～50000
Enclose, the scope of more preferably 500～10000, the scope of most preferably 500～3000.If the Mn of above-mentioned (E) is above-mentioned scope,
Then melt viscosity is the scope of appropriateness, it can be ensured that good workability.
The melt viscosity of 50 DEG C recorded according to JIS Z8803 of above-mentioned urethane acrylate oligomer (E) is excellent
Elect the scope of 500～200000mPa s, the scope of more preferably 500～100000 as.Melted during 50 DEG C of above-mentioned if (E)
Viscosity is above-mentioned scope, then workability is excellent, can cut down the addition of solvent, therefore can obtain high productivity ratio.
It addition, make above-mentioned NCO terminal carbamate ester prepolymer (C) and there is (methyl) propylene of hydroxyl
When acid compounds (D) carries out urethane reaction, can be without catalyst or there is urethanation catalyst
Under the conditions of carry out, and be not particularly limited.The reaction of above-mentioned urethane preferably occurs in the NCO in reactant
Content (%) substantially achieve constant till.
In the case of using above-mentioned urethanation catalyst, can be in any stage of urethane reaction
Suitably it is added.As above-mentioned urethanation catalyst, it is possible to use known catalyst, such as, can list three
Organic gold such as the nitrogen-containing compounds such as ethamine, triethylenediamine, N-methylmorpholine or potassium acetate, zinc stearate, stannous octoate
Belong to the organo-metallic compound such as salt or tin dilaurate dioctyl tin, dibutyl tin laurate.
For the usage amount of above-mentioned urethanation catalyst, if safety when will not give reaction, centre
Body or the stability of goods, quality etc. bring harmful effect, are just not particularly limited.
It addition, after the completion of reaction or reaction midway, known HP catalyst killer can be added, make above-mentioned carbamic acid
The catalysis activity of esterification catalyst inactivates or suppresses it, it is achieved stablizing of reaction aspect, storage aspect, quality aspect etc.
Change.
(F) not there is the organic solvent of aromatic backbone
It follows that by above-mentioned urethane acrylate oligomer (E) and selected from ketone series solvent, amide series solvent and
At least one in haloalkyl series solvent does not have organic solvent (F) mixing of aromatic backbone, thus can obtain this
Improving eyesight target, do not contain the ultra-violet solidified urethane acrylate compositions of Photoepolymerizationinitiater initiater.
As above-mentioned ketone series solvent, such as, can list butanone, acetone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, two isobutyls
Base ketone, isophorone, 2,3-acetyl butyryl, 4-methyl-2,3-pentanedione, 5-methyl-2,3-acetyl butyryl, 2,3-pentanedione, 2-oneself
Ketone, cycloheptanone, Ketocyclopentane, 3-decanone, 2-ten diketone, 4-hydroxy-4-methyl-2-pentanone (DAA), diacetyl, 2,4-bis-
Methyl-propione, 3,4-dimethyl-1,2-cyclopentanedione, 3,5-dimethyl-1,2-cyclopentanedione, 2-hydroxyl-6-isopropyl-
3-methyl-2-cyclonene, dipropyl ketone, 3-octanone, 3-heptanone, 3-ethyl-2-hydroxyl-2-cyclopentenone, 3-nonanone, 3-are own
Ketone, 1-penten-3-one, 2-margarone, 2，3-heptanedione, 3,4-acetyl butyryl, 6,10,14-trimethyl-2-pentadecane diketone, 5-
Hexene-2-ketone, 4-hexene-3-one, 1-hexene-3-one, 2-hexyl Ketocyclopentane, 1-hydroxy-2-butanone, 4-hydroxy-2-butanone, 2-
Hydroxyl-2-cyclonene, 1-hydroxyl-2-heptanone, 3-hydroxyl-methyln-hexyl ketone, 2-hydroxyl-3,4-dimethyl-2-cyclopentenone, 2-hydroxyl
Base-propione, 1-hydroxy-4-methyl-2-pentanone, 1-hydroxy-5-methyl base-methyl-n-butyl ketone, 3-hydroxyl-2 pentanone, 6-methyl-3-heptan
Ketone, 2-methyl-3-(pentenyl)-2-cyclopentenone, 4-isopropyl-2-cyclonene, 5-isopropyl-3-nonene-2,8-bis-
Ketone, 5-isopropyl-8-methyl-6,8-nonadiene-2-ketone, 3-methyl-2-(cis-pentenyl)-2-cyclopentenone, 3-first
Base-2-(trans-pentenyl)-2-cyclopentenone, to alkane-2-ketone in the Meng, ketone in the Meng, 4-methyl-3-amylene-2-ketone, 2-heptanone, 2-
Nonanone, methyln-hexyl ketone, methyl ionone, 5 methy 12 hexanone, 3-methyl-2-butanone, 2-undecyl ketone, 2-decanone, 2 pentanone, 2-
Ten triketones, 3-butene-2-one, 3-methyl-2-cyclopentenone, 6-methyl-2-heptanone, 5-methyl-2-hepten-4-one, 3-methyl-
Methyl-n-butyl ketone, 3-methyl-2 pentanone, Alpha-Methyl ionone, 3-methyl isophthalic acid, 2-cyclohexanedione, 3-methyl cyclohexanone, 3-methyl ring ten
Five alkanone, 6-methyl-3,5-heptadiene-2-ketone, 6-methyl-methyl heptenone, 3-methyl-2,4-nonyl diketone, 4-nonanone, 3-
Nonene-2-ketone, 3,5-octadiene-2-ketone, 1,5-octadiene-3-ketone, 3-octene-2-ketone, 1-octene-3-ketone, 2-octene-4-
Ketone, 4-ketoisophorone, 2-pentadecanone, propione, 3-amylene-2-ketone, 4-hydroxyhexane-3-ketone, 1-(1-Foxlene-
6-yl)-1-acetone, 2-propiono pyrroles, raspberry ketone, 4-tbutylcyclohexanone, 4-t-pentylcyclohexanone, 2-tetradecane ketone,
Tetramethyl cyclohexyl ketenes, 12-tridecylene-2-ketone, 3,5,5-trimethyl-1,2-cyclohexanedione, 1-(2,4,4-trimethyls-
2-cyclohexenyl group)-trans-2-butene-1-ketone, 2-hydroxyl-2,6,6-trimethylcyclohexanones, 2,2,6-trimethylcyclohexanones, 3,
3,5-trimethylcyclohexanones, 2,3-hendecane diketone, 6-hydroxyl-5-decanone, verbenone, 1,10-hendecene-2-ketone, 2,
2,6-trimethyls-Isosorbide-5-Nitrae-cyclohexanedione, 2,3-acetyl caproyl, 2, oneself fork base of 5-acetyl butyryl, 2-cyclonene, 2-hepten-4-one, 2-
Ketocyclopentane, 2-methyl-propione, 3,5,5-trimethyl-4-methylene-2-cyclonenes, 4-(2,3,6-trimethylphenyl)-3-
Butene-2-one, 4,5-acetyl caproyl, 4,7-dimethyl-6-octene-3-ketone, 5,6-diketone in the last of the ten Heavenly stems, 5-methyl-5-hexene-2-ketone, 6-
Methyl-4,5-heptadiene-2-ketone, 6-hydroxyl carvone, 7-octene-2-ketone, 8-nonene-2-ketone, 3-ethyl-2-hydroxyl-4-first
Base-2-cyclopentenone, 2-hexyl-2-cyclopentenone, 8-hydroxyl-4-Foxlene-3-ketone, butyl ketone etc..At these ketone series solvents
In, preferably butanone, acetone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, diisobutyl ketone, isophorone.
As above-mentioned amide series solvent, such as, can list dimethylformamide, N,N-dimethylacetamide, alcoxyl
Base-N-isopropyl-aliphatic amide series solvent such as propionic acid amide., hydroxyalkylamides or METHYLPYRROLIDONE, N-second
The cycloaliphatic amide series solvents such as base-ketopyrrolidine.In these amide series solvents, preferably dimethylformamide.
As above-mentioned haloalkyl series solvent, for the organic solvents such as fluorine system, chlorine series solvent, bromine system, iodine system, wherein preferred chlorine
It it is organic solvent.As above-mentioned chlorine-based organic solvent, such as, can list dichloromethane, chloroform, trichloro ethylene, four chloroethenes
Alkene, carbon tetrachloride, 1,2-dichloroethanes, 1，1，1-trichloroethane etc., more preferably dichloromethane, chloroform.
Only use not using the above-mentioned organic solvent (F) without aromatic backbone there is the organic of aromatic backbone
In the case of solvent, or in the case of the above-mentioned organic solvent with aromatic backbone of a large amount of use, it is impossible to fully show
Go out ultra-violet solidified, the performances such as viscosity that disappear of applicator surface, thus the purpose of the present invention cannot be realized.
In the above-mentioned organic solvent (F) without aromatic backbone, ketone series solvent is in terms of realizing the purpose of the present invention
Can more effectively play a role, the most preferably.
In ultra-violet solidified urethane acrylate compositions used in the present invention, above-mentioned do not have fragrance
The scope that containing ratio is 0.2～80 mass % of the organic solvent (F) of race's skeleton.
If above-mentioned in above-mentioned ultra-violet solidified urethane acrylate compositions does not have aromatic backbone
The containing ratio of organic solvent (F) is above-mentioned scope, then can form smooth coating and uniform film, and can be at ultraviolet
Solidify efficiently during irradiation, solidification inequality will not occur.
The above-mentioned organic solvent (F) without aromatic backbone if mixing use known method, and do not have
It is particularly limited to.
The known normally used Photoepolymerizationinitiater initiater (such as, 1-hydroxycyclohexylphenylketone etc.) with aromatic structure
Decompose because the light of aromatic structure absorbs, produce free radical, Photoepolymerizationinitiater initiater after decomposition occur in conjunction with, now, become
For the quinoid structure that yellow chromaticity is high.
In the present invention, it is considered to by not using Photoepolymerizationinitiater initiater and use not to have aromatic backbone
Organic solvent (F), thus carry out ultraviolet curing reaction in the same manner as the situation employing Photoepolymerizationinitiater initiater, now, presumption
Different from the situation employing Photoepolymerizationinitiater initiater and do not produce quinoid structure, therefore, solidfied material generation xanthochromia will not be made, can
To obtain without xanthochromia and the formed body of transparency excellence, film etc..
In the case of above-mentioned ultra-violet solidified urethane acrylate compositions has NCO, permissible
Either phase in manufacturing process, coordinates the reactive compounds of the functional group with non-aromatic skeleton as firming agent.
As above-mentioned firming agent, such as, can list aliphatic polyol, alicyclic polyol, aliphatic polyamine, alicyclic polyamine
Deng.
The hydroxyl of the polyhydric alcohol used as firming agent and ultra-violet solidified urethane acrylate compositions
In NCO mol ratio, i.e., (NCO/OH mol ratio) be preferably the scope of 0.7/1.0～20/1.0, more preferably
～the scope of 10/1.0, the more preferably scope of 0.9/1.0～5/1.0, most preferably 0.9/1.0～1.1/ 0.7/1.0
1.0.If above-mentioned (NCO/OH mol ratio) is above-mentioned scope, then curing reaction can be made efficiently and well to carry out.
In the ultra-violet solidified urethane acrylate compositions of the present invention, except above-mentioned carbamate propylene
Beyond acid esters oligomer (E), it is also possible to without departing from using in the range of the purpose of the present invention, not there is the third of aromatic backbone
Alkene acrylic monomer.As aforesaid propylene acrylic monomer, such as, can list: (methyl) acrylic acid；(methyl) acrylic acid methyl ester.,
(methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl)
Sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 1-Octyl acrylate, (methyl) propylene
Acid different monooctyl ester, (methyl) 2-EHA, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) third
The Arrcostab of (methyl) the acrylic acid C1-24 such as olefin(e) acid stearyl ester；(methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester etc.
(methyl) acrylate ester；(methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) propylene
Acid bicyclopentyl epoxide ethyl ester, (methyl) acrylic acid norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring last of the ten Heavenly stems
The endocyclics such as ester (methyl) acrylate；(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) propylene
(methyl) dihydroxypropyl C2-10 Arrcostab or C2-10 alkane diol list (methyl) acrylate such as acid hydroxybutyl ester；(first
Base) (methyl) the acrylic acid fluorine such as acrylic acid trifluoro ethyl ester, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro isopropyl ester
For C1-10 Arrcostab；(methyl) alkoxyalkyl acrylates such as (methyl) methoxyethyl acrylate；Polyethyleneglycol (first
Base) polyalkylene glycol mono (methyl) acrylate such as acrylate；The alkane polyols such as glycerol list (methyl) acrylate
Single (methyl) acrylate；(methyl) acrylic acid 2-dimethylamino ethyl ester, (methyl) acrylic acid 2-diethylamino ethyl ester,
(methyl) acrylic acid 2-t-butylaminoethyl etc. has (methyl) acrylate of amino；(methyl) glycidyl
Ester, (methyl) allyl acrylate；Ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,3-the third two
Alcohol two (methyl) acrylate, BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-oneself
Alkane diol two (methyl) acrylate such as glycol two (methyl) acrylate；The alkane such as glycerol two (methyl) acrylate are many
Unit's alcohol two (methyl) acrylate；Diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, poly-second two
The poly-alkylenes such as alcohol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate
Base glycol two (methyl) acrylate；Two (methyl) acrylic acid of the modified alkane polyol of the acid such as fatty acid modified tetramethylolmethane
Ester；Endocyclic two (methyl) acrylate, the trimethylolpropane tris (first such as Tricyclodecane Dimethanol two (methyl) acrylate
Base) acrylate, glycerol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl)
Acrylate, tetramethylol methane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six
Alkane polyol (methyl) acrylate such as (methyl) acrylate；The C2-of the alkane polyol such as trimethylolpropane, glycerol
Three (methyl) acrylate of 4 alkylene oxide addition products；Three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate etc. have
There is three (methyl) acrylate etc. of triazine ring.They can be used alone, it is also possible to combines two or more and uses.
In above-mentioned ultra-violet solidified urethane acrylate compositions, in addition to above-mentioned raw materials, it is also possible to
In the range of the purpose of the present invention, any stage of manufacturing process uses various additive.
As above-mentioned additive, such as, can use surfactant, antioxidant, deaeration agent, abrasive particle, filler, pigment, dye
Material, coloring agent, thickening agent, surfactant, fire retardant, plasticizer, lubricant, antistatic agent, heat-resisting stabilizing agent, viscosifier,
The known additive such as curing catalysts, stabilizer, silane coupler, wax.It addition, as required, can not hindered this
In the range of bright purpose, suitably select and use existing known thermoplastic resin, heat-curing resin etc. to be used as mixing
Use resin.It should be noted that above-mentioned additive is only an example, as long as not hindering the purpose of the present invention, the most existing fixed
Its kind and usage amount.
As above-mentioned viscosifier, such as can use rosin series resin, rosin ester system resin, hydrogenated wood rosin glycerol ester system resin,
Terpenic series resin, terpenes phenol resin, hydriding terpene system resin, or the C as Petropols5The group aliphatic resin of system, C9System
Aromatic resin and C5System and C9The copolymer resins etc. of system.
As above-mentioned plasticizer, such as, can use dibutyl phthalate, dioctyl phthalate, O-phthalic
Acid dicyclohexyl maleate, diisooctyl phthalate, diisooctyl phthalate, dibenzyl phthalate, phthalic acid
Butyl benzyl ester, trioctyl phosphate, epoxy plasticizer, toluene-sulf amide, chlorinated paraffin, adipate ester, Oleum Ricini etc..Permissible
Enumerate acid phosphate methyl ester (methyl acid phosphate) (AP-1), acrylic acid series surface conditioner (BYK-361N) etc..
As aforementioned stable agent, such as, can use hindered phenol based compound, benzotriazole based compound, hindered amine system
Compound etc..
As above-mentioned packing material, such as, can use silica derivative, Talcum, metal powder, calcium carbonate, clay, white carbon black
Deng.
The situation making above-mentioned ultra-violet solidified urethane acrylate compositions solidify is irradiated utilizing ultraviolet
Under, such as can use mercury lamp (low pressure, high pressure, supertension etc.), hydrogen lamp, deuterium lamp, Halogen light, xenon lamp, carbon arc lamp, fluorescent lamp,
The various light sources such as He-Cd laser, wherein, preferably high voltage mercury lamp.
<film shaped body>
Film shaped body described in the present invention is to have on base material by employing above-mentioned ultra-violet solidified amino
The film shaped body of cured coating film obtained by the manufacture method of the cured coating film of formic acid esters acrylate composition.Above-mentioned ultraviolet
Although curable urethane acrylate compositions does not contains any Photoepolymerizationinitiater initiater, but has and irradiate based on ultraviolet
And the rapidly-curable brought, do not exist cured coating film through time xanthochromia, do not exist caused by unreacted reactant or analyte right
The pollution of contactant, and there is the performances such as the screening characteristics of excellence, the transparency, formability, it is thus possible, for instance at film shaped body
The broad range such as (film, sheet), fiber, application, fixative, packaging material, grinding agent, road pavement agent, electric material
In field useful.
Wherein, as film shaped body, such as, can list the optics components such as light guiding film (light-guiding film), light guide sheet.
The blooming of the present invention is to have by employing the combination of above-mentioned ultra-violet solidified urethane acrylate
The blooming of cured coating film obtained by the manufacture method of the cured coating film of thing, for the blooming below thickness 200 μm, its
Transmitance is excellent, such as the total light transmittance recorded according to JIS K7361-1 during thickness 100 μm of blooming be 92% with
On, therefore it is for example suitable for light guiding film (light-guiding film) etc..
It should be noted that in the present invention, as the most generally exhaled as title, it is below 200 μm by thickness
Goods are defined as " film ", and more than the goods of 200 μm, thickness is defined as " sheet ".
<manufacture method of film shaped body>
The manufacture method of the film shaped body of the present invention is to have the manufacture method by above-mentioned cured coating film on base material
Obtained by the manufacture method of film shaped body of cured coating film, can list: by above-mentioned ultra-violet solidified carbamate
Acrylate composition is coated on base material and forms film, irradiation ultraviolet radiation and make above-mentioned curing of coating, then, make above-mentioned not
There is organic solvent (F) volatilization of aromatic backbone, obtain the scope of preferably 10～1000 μm, more preferably 15～600 models of μm
The method etc. of the solidfied material (such as film, sheet etc.) of the lower thickness enclosed.
As above-mentioned base material, such as, can list metal (plate, paper tinsel etc.), plastics (plate, sheet, film etc.), paper (processing release paper
Deng), glass, pottery, wood-block (cosmetic version etc.), pottery etc..
If the manufacture method of the film shaped body of the present invention is carried out example, as follows including such as can be listed
The method of a series of operation of (operation 1)～(operation 2).
The preparation of (operation 1) ultra-violet solidified urethane acrylate compositions
In reaction vessel, put into the polyhydric alcohol (A) without aromatic backbone of molten condition, start stirring.Connect down
Coming, marginal not meaning heat radiation limit puts into the polyisocyanate (B) without aromatic backbone of ormal weight, makes interior temperature rise to regulation temperature
After degree, stir the stipulated time at such a temperature, obtain molecular end and there is the carbamate prepolymer (C) of NCO.
It follows that add the polymerization inhibitor of ormal weight and there is (methyl) acrylic compounds (D) of hydroxyl, continue reaction
After stipulated time, obtain the urethane acrylate oligomer as the molecular end of target with (methyl) acryloyl group
(E)。
Afterwards, add the organic solvent (F) without aromatic backbone as adjustment liquid to adjust melt viscosity, can obtain
Ultra-violet solidified urethane acrylate compositions to the present invention.
The manufacture of (operation 2) film shaped body
Utilize the ultra-violet solidified urethane acrylate combination that knife type coater will obtain in above-mentioned (operation 1)
Thing is coated on the regulation of below polyethylene terephthalate (PET) film up to thickness 200 μm implementing demoulding process
Thickness and form film, utilize high voltage mercury lamp with have nitrogen purging (purge) device ultraviolet lamp to irradiate purple
Outside line, so that above-mentioned curing of coating.
Then, after above-mentioned cured coating film carries out at 60 DEG C the ripening of stipulated time, make above-mentioned organic solvent (F) wave
Send out, the film of the film shaped body as the cured coating film on base material with the present invention can be obtained.
Embodiment
Hereinafter, utilizing embodiment more specifically to illustrate the present invention, the scope of the present invention is not limited to these
Embodiment.
It addition, in the present invention, unless otherwise specified, then " part " be " mass parts ", " % " be " quality % ".
It should be noted that the assay method and the evaluation methodology that use in the present invention are as follows.
(assay method of the isocyanate equivalent of NCO terminal carbamate ester prepolymer (C))
Isocyanate equivalent (unit: the g/ of NCO terminal carbamate ester prepolymer (C) used in the present invention
Eq) for the value recorded according to JIS K7301.
Specifically, in conical flask, the sample of accurate weighing carbamate prepolymer (C), makes it molten by dry toluene
Solve, add after di-n-butyl amine aqueous solution 10ml so that it is homogeneous then stand, use bromocresol green as indicator, use 0.5 equivalent
The standard solution of hydrochloric acid is neutralized titration to be carried out quantitatively.
(assay method of the melt viscosity of urethane acrylate oligomer (E))
According to JIS Z8803, use Digital Viscometer (Tokyo Keiki Inc.'s system, model: DVM-BII), to enforcement
The melt viscosity of the urethane acrylate oligomer (E) obtained in example and comparative example (measure temperature: 50 DEG C, unit:
MPa s) it is measured.
(evaluation methodology of ultra-violet solidified (disappear viscosity) and determinating reference)
Utilize knife type coater, the ultra-violet solidified urethane acrylate that will obtain in embodiment and comparative example
Compositions is coated on to implement and forms film on polyethylene terephthalate (PET) film that the demoulding processes, and use has
High voltage mercury lamp 1 lamp of 120w/cm, the ultraviolet lamp " N of nitrogen purging device2Sweeping type irradiates with the UV of conveyer belt
Device " (Co., Ltd.'s GS YUASA system), irradiating light quantity 0.8J/cm2, shine under conditions of (oxygen concentration 1%) under nitrogen atmosphere
Penetrate ultraviolet, so that above-mentioned curing of coating.
Afterwards, heat 10 minutes at temperature 60 ± 5 DEG C further, make used organic solvent volatilize, obtain conduct
Base material has the film (film of thickness 100 μm) of the film shaped body of cured coating film.
Touched by finger and confirm that the top layer (surface) of above-mentioned film, with or without tacky, is commented according to following benchmark
Valency.
The determinating reference of ultra-violet solidified (disappear viscosity)
Zero: without tacky, in the case of the unattached fraction of finger, ultra-violet solidified excellence.
×: have tacky, in the case of finger attachment fraction, ultra-violet solidified difference.
(evaluation methodology of yellow chromaticity and determinating reference)
Utilize multiple light courcess spectral photometric colour measuring meter (SUGA testing machine Co., Ltd. system), to the film obtained in embodiment and comparative example
The yellowness index (YI of thickness direction0) be measured, it is evaluated according to following benchmark.
The determinating reference of yellow chromaticity
Zero: at the YI of thickness direction0In the case of being less than 0.6, yellowing resistance is excellent.
×: at the YI of thickness direction0In the case of 0.6, yellowing resistance is poor.
(evaluation methodology of discoloration-resistant and determinating reference)
Being exposed in drying machine by the above-mentioned film made 120 DEG C × 72 hours, (SUGA tries to utilize multiple light courcess spectral photometric colour measuring meter
Yan Ji Co., Ltd. system) to yellow chromaticity (yellowness index: the YI after exposing1) be measured, it is evaluated according to following benchmark.
The determinating reference of discoloration-resistant
Zero: the YI of thickness direction1In the case of being less than 2.0, discoloration-resistant is excellent.
×: the YI of thickness direction1In the case of 2.0, discoloration-resistant is poor.
(evaluation methodology of the transparency and determinating reference)
Use Japan electricity Se Industrial Co., Ltd NDH-2000, according to total to the above-mentioned film made of JIS K7361-1
Light transmittance (%) is measured, and is evaluated according to following benchmark.
The determinating reference of the transparency
Zero: in the case of total light transmittance is more than 92%, the transparency is excellent.
×: in the case of total light transmittance is less than 92%, the transparency is poor.
(synthesis example 1)
" synthesis of urethane acrylate oligomer (E1) "
In reaction vessel, as not having the polyhydric alcohol (A) of aromatic backbone, and put into the poly-of the molten condition of 50 DEG C
Oxygen tetramethylene glycol (trade name: PTMG-1000, Mitsubishi chemical Co., Ltd's system, Mn are 1000) 114 mass parts, start to stir
Mix.
It follows that as not having the polyisocyanate (B) of aromatic backbone, and add 4,4 '-dicyclohexyl methyl hydride two
Isocyanates (following, it is abbreviated as " H12MDI”.) 100 mass parts, after marginal not meaning heat radiation limit makes interior temperature rise to 85 DEG C, limit keeps
Temperature limit is stirred 3 hours, obtains molecular end and has the carbamate prepolymer (C) of NCO.
Further, marginal not meaning heat radiation limit is slowly added to acrylic acid 2-hydroxy methacrylate 62 mass parts and is used as having hydroxyl
(methyl) acrylic compounds (D), stirs 2 hours at 85 DEG C, obtains urethane acrylate oligomer (E1).
(synthesis example 2～6)
" urethane acrylate oligomer (E2)～the synthesis of (E6) "
Change as shown in table 1 used polyhydric alcohol (A), polyisocyanate (B), there is (methyl) acrylic compounds of hydroxyl
Compound (D) respective kind and usage amount, in addition, obtain carbamic acid by the reaction condition as synthesis example 1
Ester acrylate oligomer (E2)～(E6).
[table 1]
| Table 1 | Synthesis example 1 | Synthesis example 2 | Synthesis example 3 | Synthesis example 4 | Synthesis example 5 | Synthesis example 6 |
| The synthesis material (mass parts) of urethane acrylate oligomer (E) | (E1) | (E2) | (E3) | (E4) | (E5) | (E6) |
| PTMG-1000 | 114 | 81 | 114 | 114 | 114 | 123 |
| Acrylic acid 2-hydroxy methacrylate | 62 | 71 | 65 | |||
| Acrylic acid 4-hydroxybutyl | 87 | |||||
| Acrylic acid 2-hydroxy methacrylate | 70 | |||||
| Pentaerythritol triacrylate | 185 | |||||
| Tetramethylol methane tetraacrylate | 79 | |||||
| H12MDI | 100 | 100 | 100 | 100 | ||
| IPDI | 100 | |||||
| MDI | 100 |
It should be noted that writing a Chinese character in simplified form in table 1 represents following title.
PTMG-1000: polyoxytetramethylene glycol (trade mark: Mitsubishi chemical Co., Ltd's system, number-average molecular weight 1000)
H12MDI:4,4 '-dicyclohexyl methyl hydride diisocyanate
IPDI: isophorone diisocyanate
MDI:4,4 '-methyl diphenylene diisocyanate
(embodiment 1)
Weigh urethane acrylate oligomer (E1) 100 mass parts obtained in synthesis example 1 in the mixing container
With the butanone as organic solvent (F) (hereinafter referred to as " MEK ".) 20 mass parts, at room temperature mix to uniformly, prepare
Ultra-violet solidified urethane acrylate compositions.
Utilize knife type coater, the ultra-violet solidified urethane acrylate compositions of above-mentioned preparation is coated on
Film is formed on polyethylene terephthalate (PET) stripping film processed.
After coating, immediately with having high voltage mercury lamp 1 lamp of 120w/cm, the ultraviolet lamp of nitrogen purging device,
Irradiate light quantity 0.8J/cm2, carry out ultraviolet irradiation under nitrogen atmosphere (oxygen concentration less than 1%), so that above-mentioned film is solid
Change.Further, heat 10 minutes at 60 DEG C in an oven, make organic solvent volatilize, make as having solidification on base material
The film (P1) (thickness 100 μm) of the film shaped body of film.
(embodiment 2～9 and comparative example 1～8)
As shown in table 2 and table 3, change used prepolymer, the kind of organic solvent, Photoepolymerizationinitiater initiater presence or absence with
Kind and usage amount, in addition, operate similarly to Example 1, prepares ultra-violet solidified carbamate third respectively
Alkene acid ester composite, to above-mentioned ultra-violet solidified urethane acrylate compositions irradiation ultraviolet radiation, produces thickness
The film (P2) of 100 μm～(P17).
[table 2]
| Table 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| The mark of urethane acrylate oligomer (E) | (E1) | (E1) | (E1) | (E1) | (E2) | (E3) | (E4) | (E5) | (E1) |
| Not there is the polyhydric alcohol (A) of aromatic backbone | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG-1000 |
| Not there is the polyisocyanate (B) of aromatic backbone | H12MDI | H12MDI | H12MDI | H12MDI | H12MDI | H12MDI | IPDI | H12MDI | H12MDI |
| There is (methyl) acrylic compounds (D) of hydroxyl | HEA | HEA | HEA | HEA | 4HBA | HEMA | HEA | PR3A/ PE4A | HEA |
| Not there is the kind of the specific organic solvent (F) of Fang Hun race skeleton | MEK | MIBK | Dichloromethane Alkane | MEK | MEK | MEK | MEK | MEK | MEK |
| Melt viscosity (the mPa of urethane acrylate oligomer (E) s、50℃) | 29000 | 29000 | 29000 | 29000 | 17000 | 15000 | 14000 | 25000 | 29000 |
| Urethane acrylate oligomer (E) (mass parts) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Not there is the specific organic solvent (F) (mass parts) of aromatic backbone | |||||||||
| Butanone | 20 | 1 | 20 | 20 | 15 | 20 | 300 | ||
| Methyl iso-butyl ketone (MIBK) | 20 | ||||||||
| Dichloromethane | 20 | ||||||||
| Organic solvent (mass parts) beyond specific organic solvent (F) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Organic solvent/(organic solvent+oligomer (E)) × 100 (quality %) | 16.7 | 16.7 | 16.7 | 1.0 | 16.7 | 16.7 | 13.0 | 16.7 | 75.0 |
| Photoepolymerizationinitiater initiater | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing |
| Evaluation result | |||||||||
| Ultra-violet solidified (surface, the coated face viscosity) of resin combination | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Total light transmittance (%) of film | 92.0 | 92.0 | 92.0 | 92.0 | 92.0 | 92.0 | 92.0 | 92.0 | 92.0 |
| Yellow chromaticity (yellowness index: the YI of film0) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Yellow chromaticity (yellowness index: YI after the heat resistant test of film1) | 0.5 | 0.5 | 0.8 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
[table 3]
| Table 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| The mark of urethane acrylate oligomer (E) | (E1) | (E1) | (E1) | (E1) | (E1) | (E6) | (E1) | (E1) |
| Not there is the polyhydric alcohol (A) of aromatic backbone | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG- 1000 | PTMG-1000 | PTMG- 1000 |
| Not there is the polyisocyanate (B) of aromatic backbone | H12MDI | H12MDI | H12MDI | H12MDI | H12MDI | H12MDI | H12MDI | |
| There is the polyisocyanate (B ') of aromatic backbone | MDI | |||||||
| There is (methyl) acrylic compounds (D) of hydroxyl | HEA | HEA | HEA | HEA | HEA | HEA | HEA | HEA |
| Not there is the kind of the specific organic solvent (F) of aromatic backbone | Nothing | Nothing | Nothing | Nothing | Nothing | MEK | MEK | Nothing |
| The melt viscosity of urethane acrylate oligomer (E) (mPa s, 50℃) | 29000 | 29000 | 29000 | 29000 | 29000 | 22000 | 29000 | 29000 |
| Urethane acrylate oligomer (E) (mass parts) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Not there is the specific organic solvent (F) (mass parts) of aromatic backbone | ||||||||
| Butanone | 20 | 900 | 20 | |||||
| Organic solvent (mass parts) beyond specific organic solvent (F) | ||||||||
| Butyl acetate | 20 | 20 | ||||||
| Toluene | 20 | |||||||
| Methanol | 20 | |||||||
| Organic solvent/(organic solvent+oligomer (E)) × 100 (quality %) | 0.0 | 9.1 | 9.1 | 9.1 | 9.1 | 16.7 | 90.0 | 9.1 |
| Photoepolymerizationinitiater initiater (mass parts) | ||||||||
| 1-hydroxycyclohexylphenylketone | 3 | 3 | ||||||
| Evaluation result | ||||||||
| Ultra-violet solidified (surface, the coated face viscosity) of resin combination | Uncured | ○ | Uncured | Uncured | Uncured | × | There is solidification not All | ○ |
| Total light transmittance (%) of film | Cannot membranization | 90 | Cannot membranization | Cannot membranization | Cannot membranization | 88 | Cannot membranization | 90 |
| Yellow chromaticity (yellowness index: the YI of film0) | Cannot membranization | 1.8 | Cannot membranization | Cannot membranization | Cannot membranization | 1.8 | Cannot membranization | 1.7 |
| Yellow chromaticity (yellowness index: YI after the heat resistant test of film1) | Cannot membranization | 4.2 | Cannot membranization | Cannot membranization | Cannot membranization | 2.5 | Cannot membranization | 4.1 |
It should be noted that table 2 and table 3 write a Chinese character in simplified form the following title of expression.
HEA: acrylic acid 2-hydroxy methacrylate
4HBA: acrylic acid 4-hydroxybutyl
HEMA: 2-hydroxyethyl methacrylate
PE3A: pentaerythritol triacrylate
PE4A: tetramethylol methane tetraacrylate
MEK: butanone
MIBK: methyl iso-butyl ketone (MIBK)
MDI:4,4 '-methyl diphenylene diisocyanate
PTMG-1000: polyoxytetramethylene glycol (trade mark: Mitsubishi chemical Co., Ltd's system, number-average molecular weight 1000)
H12MDI:4,4 '-dicyclohexyl methyl hydride diisocyanate
Industrial applicability
The manufacture method of the cured coating film of the present invention is by the ultra-violet solidified amino not containing Photoepolymerizationinitiater initiater
Formic acid esters acrylate composition irradiation ultraviolet radiation and obtain cured coating film and described compositions shows the photo-curable of excellence,
And described cured coating film will not occur through time xanthochromia, the transparency is excellent, will not pollute the thing contacted with film or formed body
Body, therefore at such as optics component (film, sheet), fiber, application, fixative, packaging material, grinding agent, road pavement agent, electricity
In the broad range of field such as sub-electric material useful.
Claims (6)
1. the manufacture method of a cured coating film, it is characterised in that will there is (methyl) acryloyl group containing molecular end
Urethane acrylate oligomer (E) and in ketone series solvent, amide series solvent and haloalkyl series solvent at least
The ultra-violet solidified urethane acrylate compositions of a kind of organic solvent (F) without aromatic backbone is coated on
Form film, then irradiation ultraviolet radiation on base material, then make described organic solvent (F) volatilization obtain the solidification of cured coating film
The manufacture method of film, described urethane acrylate oligomer (E) is by making (methyl) acrylic compounds with hydroxyl
Compound (D) and molecular end have the carbamate prepolymer (C) of NCO and carry out additive reaction and obtain, institute
State carbamate prepolymer (C) by making not have the polyhydric alcohol (A) of aromatic backbone and not there is the poly-of aromatic backbone
Isocyanates (B) reacts and obtains, wherein,
Described ultra-violet solidified urethane acrylate compositions contains the described organic solvent of 0.2～80 mass %
, and do not contain Photoepolymerizationinitiater initiater (F).
The manufacture method of cured coating film the most according to claim 1, wherein, described in there is (methyl) acrylic compounds of hydroxyl
Compound (D) is for selected from (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxyl
At least one in base propyl ester, (methyl) acrylic acid 4-hydroxybutyl and pentaerythritol triacrylate.
The manufacture method of cured coating film the most according to claim 1, wherein, described organic solvent (F) be selected from butanone,
In acetone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, diisobutyl ketone, isophorone, dimethylformamide, dichloromethane and chloroform
At least one.
The manufacture method of cured coating film the most according to claim 1, wherein, described urethane acrylate oligomer
(E) according to the scope that the melt viscosity at 50 DEG C measured by JIS Z8803 is 500～100000mPa s.
5. a blooming, it is characterised in that be that there is the system by the cured coating film according to any one of Claims 1 to 4
Make method and the blooming of prepared cured coating film, wherein,
Described blooming is more than 92% when thickness is 100 μm according to the total light transmittance measured by JIS K7361-1.
6. the manufacture method of a film shaped body, it is characterised in that be to have on base material by appointing in Claims 1 to 4
The manufacture method of one described cured coating film and the manufacture method of the film shaped body of prepared cured coating film,
Wherein, described ultra-violet solidified urethane acrylate compositions is coated on base material and forms film,
Irradiation ultraviolet radiation and make described curing of coating, then make described organic solvent (F) volatilize.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-080356 | 2012-03-30 | ||
| JP2012080356 | 2012-03-30 | ||
| PCT/JP2013/056480 WO2013146193A1 (en) | 2012-03-30 | 2013-03-08 | Ultraviolet light curing urethane acrylate composition, thin-film formed body, optical film, and method for manufacturing thin-film formed body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104105730A CN104105730A (en) | 2014-10-15 |
| CN104105730B true CN104105730B (en) | 2016-08-24 |
Family
ID=49259461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380008738.6A Active CN104105730B (en) | 2012-03-30 | 2013-03-08 | The manufacture method of cured coating film, blooming and the manufacture method of film shaped body |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5516829B2 (en) |
| KR (1) | KR101575698B1 (en) |
| CN (1) | CN104105730B (en) |
| TW (1) | TWI472547B (en) |
| WO (1) | WO2013146193A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014045782A1 (en) * | 2012-09-20 | 2014-03-27 | Dic株式会社 | Ultraviolet curable urethane acrylate composition, thin film molded body, optical film and method for manufacturing thin film molded body |
| JP6609148B2 (en) * | 2015-09-17 | 2019-11-20 | 中国塗料株式会社 | Energy ray curable resin composition for flooring, coated flooring, method for producing coated flooring and antifouling method for flooring |
| JP6292242B2 (en) * | 2016-01-27 | 2018-03-14 | 岩崎電気株式会社 | Curing method and curing system |
| JP7359520B2 (en) * | 2018-02-22 | 2023-10-11 | ビーエーエスエフ ソシエタス・ヨーロピア | Polyurethane-based polymer material with excellent thermal deformation resistance and tear elongation |
| CN111057215B (en) * | 2018-10-16 | 2021-09-21 | 比亚迪股份有限公司 | Polyurethane resin composition, fiber resin composite material, and preparation method and application thereof |
| KR102124853B1 (en) | 2018-12-14 | 2020-06-19 | 건국대학교 산학협력단 | UV-curable urethane acrylate polymer using mixture of polyester polyols and process for the preparation thereof |
| KR20210045685A (en) * | 2019-10-17 | 2021-04-27 | 현대자동차주식회사 | Uv curable resin composition capable be used for thermoforming and a replica film of real material comprising the same |
| JP2021080364A (en) * | 2019-11-19 | 2021-05-27 | スリーエム イノベイティブ プロパティズ カンパニー | Radiation curable inkjet ink, decorative sheet, and method of producing decorative sheet |
| CN112708151B (en) * | 2020-12-25 | 2023-03-17 | 宁波长阳科技股份有限公司 | Thermoplastic polyurethane elastomer film and method for making same |
| CN118027806B (en) * | 2024-02-01 | 2024-08-09 | 江苏大自然智能家居有限公司 | Water-based UV (ultraviolet) photo-curing coating for wood floor and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2837233B2 (en) * | 1990-04-27 | 1998-12-14 | 三井化学株式会社 | Radiation-curable resin and coating composition thereof |
| CA2141715C (en) * | 1994-02-08 | 1999-09-14 | Bruce A. Gruber | Organic solvent free urethane/acrylic polymer laminating adhesive for flexible packaging |
| JP2001058470A (en) * | 1999-08-20 | 2001-03-06 | Oji Paper Co Ltd | Thermal transfer recording sheet |
| WO2002006859A1 (en) * | 2000-07-18 | 2002-01-24 | Omron Corporation | Light diffusing films |
| JP3988111B2 (en) * | 2001-05-07 | 2007-10-10 | 日産自動車株式会社 | Acrylic urethane paint composition |
| JP2004217809A (en) * | 2003-01-16 | 2004-08-05 | Mitsubishi Chemicals Corp | Active energy beam-cured resin sheet |
| JP5534125B2 (en) * | 2007-10-30 | 2014-06-25 | スリーボンドファインケミカル株式会社 | Curable sheet composition |
| JP5608852B2 (en) * | 2010-04-12 | 2014-10-15 | サンノプコ株式会社 | UV curable composition |
| JP5558257B2 (en) * | 2010-08-06 | 2014-07-23 | 株式会社昭和インク工業所 | Curable composition |
| JP5739209B2 (en) * | 2011-04-05 | 2015-06-24 | 株式会社カネカ | Novel photosensitive resin composition and use thereof |
| JP2013028675A (en) * | 2011-07-27 | 2013-02-07 | Hitachi Chemical Co Ltd | Circuit connection material, and circuit connection structure using the same |
-
2013
- 2013-03-08 CN CN201380008738.6A patent/CN104105730B/en active Active
- 2013-03-08 KR KR1020147011371A patent/KR101575698B1/en active IP Right Grant
- 2013-03-08 WO PCT/JP2013/056480 patent/WO2013146193A1/en active Application Filing
- 2013-03-08 JP JP2013534093A patent/JP5516829B2/en active Active
- 2013-03-21 TW TW102109965A patent/TWI472547B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| TW201343698A (en) | 2013-11-01 |
| JP5516829B2 (en) | 2014-06-11 |
| KR20140118981A (en) | 2014-10-08 |
| TWI472547B (en) | 2015-02-11 |
| WO2013146193A1 (en) | 2013-10-03 |
| CN104105730A (en) | 2014-10-15 |
| JPWO2013146193A1 (en) | 2015-12-10 |
| KR101575698B1 (en) | 2015-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104105730B (en) | The manufacture method of cured coating film, blooming and the manufacture method of film shaped body | |
| CN104619735B (en) | Ultra-violet solidified urethane acrylate composition, film shaped body, blooming and the manufacture method of film shaped body | |
| KR102051917B1 (en) | Active energy ray-curable composition for interlayer filler | |
| EP2945973B2 (en) | Radiation curable aqueous compositions with reversible drying | |
| JP5564949B2 (en) | Curable composition | |
| TWI545138B (en) | Activation-energy-ray-curable resin composition | |
| WO2020054582A1 (en) | Urethane (meth)acrylate, active energy ray-curable composition containing same, and cured product of said composition | |
| JP2014024880A (en) | Uv-curable urethane acrylate resin composition, thin film molded article, optical film, and production method of thin film molded article | |
| EP2463346A1 (en) | UV-curable ink | |
| JP2010215774A (en) | Curable composition and method for preparing urethane (meth)acrylate | |
| JP6899225B2 (en) | Active energy ray-curable composition | |
| KR101109937B1 (en) | Ultra violet-curable paint composition | |
| CN107406563B (en) | Curable resin composition for interlayer filling | |
| CN110446736A (en) | Polyurethane (methyl) acrylate polymer | |
| JP2013023631A (en) | Active energy ray-curable hard coat agent composition, cured coating film and molded article | |
| JP7257815B2 (en) | Urethane (meth)acrylate, active energy ray-curable composition containing the same, and cured product thereof | |
| US20240317680A1 (en) | Urethane (meth)acrylate | |
| JP2013082940A (en) | Method for producing urethane (meth)acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |